Redox Reactivity of Colloidal Nanoceria and Use of Optical Spectra as an In Situ Monitor of Ce Oxidation States.

Nanoscale cerium oxide is of increasing interest in catalysis, biomedicine, renewable energy, and many other fields. Its versatility derives from the ability to form nonstoichiometric oxides that include both Ce3+ and Ce4+ ions. This work describes oxidation and reduction reactivity of colloidal cerium oxide nanocrystals, termed nanoceria, under very mild solution conditions. For instance, the as-prepared nanoceria oxidizes hydroquinone to benzoquinone, with reduction of some of the Ce4+ ions. Highly reduced nanoceria, prepared by UV irradiation in the presence of ethanol, oxidize hydroquinone back to benzoquinone. This and related reactivity allow tuning of the average cerium oxidation state in the nanocrystals without changes in size or other properties. The amounts of Ce3+ and Ce4+ in the nanoceria were determined both by X-ray absorption spectroscopy and from the stoichiometry of the reactions, measured using 1H NMR spectroscopy. The results demonstrate, for the first time, that the optical absorbance of nanoceria is linearly related to the percent Ce3+ in the sample. The decrease in absorption (blue-shift of the band edge) is due to increasing amounts of Ce3+, not to a quantum confinement effect. These findings demonstrate the facile solution reactivity of nanoceria and establish UV-visible spectroscopy as a powerful new tool for in situ determination of Ce oxidation states in ceria nanomaterials.

Concerted Growth and Ordering of Cobalt Nanorod Arrays as Revealed by Tandem in Situ SAXS-XAS Studies.

The molecular and ensemble dynamics for the growth of hierarchical supercrystals of cobalt nanorods have been studied by in situ tandem X-ray absorption spectroscopy-small-angle X-ray scattering (XAS-SAXS). The supercrystals were obtained by reducing a Co(II) precursor under H2 in the presence of a long-chain amine and a long-chain carboxylic acid. Complementary time-dependent ex situ TEM studies were also performed. The experimental data provide critical insights into the nanorod growth mechanism and unequivocal evidence for a concerted growth-organization process. Nanorod formation involves cobalt nucleation, a fast atom-by-atom anisotropic growth, and a slower oriented attachment process that continues well after cobalt reduction is complete. Smectic-like ordering of the nanorods appears very early in the process, as soon as nanoparticle elongation appears, and nanorod growth takes place inside organized superlattices, which can be regarded as mesocrystals.

Understanding the Solution and Solid-State Structures of Pd and Pt PSiP Pincer-Supported Hydrides.

The PSiP pincer-supported complex ((Cy)PSiP)PdH [(Cy)PSiP = Si(Me)(2-PCy2-C6H4)2] has been implicated as a crucial intermediate in carboxylation of both allenes and boranes. At this stage, however, there is uncertainty regarding the exact structure of ((Cy)PSiP)PdH, especially in solution. Previously, both a Pd(II) structure with a terminal Pd hydride and a Pd(0) structure featuring an η(2)-silane have been proposed. In this contribution, a range of techniques were used to establish that ((Cy)PSiP)PdH and the related Pt species, ((Cy)PSiP)PtH, are true M(II) hydrides in both the solid state and solution. The single-crystal X-ray structures of ((Cy)PSiP)MH (M = Pd and Pt) and the related species ((iPr)PSiP)PdH [(iPr)PSiP = Si(Me)(2-P(i)Pr2-C6H4)2] are in agreement with the presence of a terminal metal hydride, and the exact geometry of ((Cy)PSiP)PtH was confirmed using neutron diffraction. The (1)H and (29)Si{(1)H}NMR chemical shifts of ((Cy)PSiP)MH (M = Pd and Pt) are consistent with a structure containing a terminal hydride, especially when compared to the chemical shifts of related pincer-supported complexes. In fact, in this work, two general trends relating to the (1)H NMR chemical shifts of group 10 pincer-supported terminal hydrides were elucidated: (i) the hydride shift moves downfield from Ni to Pd to Pt and (ii) the hydride shift moves downfield with more trans-influencing pincer central donors. DFT calculations indicate that structures containing a M(II) hydride are lower in energy than the corresponding η(2)-silane isomers. Furthermore, the calculated NMR chemical shifts of the M(II) hydrides using a relativistic four-component methodology incorporating all significant scalar and spin-orbit corrections are consistent with those observed experimentally. Finally, in situ X-ray absorption spectroscopy (XAS) was used to provide further support that ((Cy)PSiP)MH exist as M(II) hydrides in solution.

Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N,N-Dimethylformamide.

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O2 + 4e(-) + 4H(+) ⇋ 2H2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc(+/0)) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the free energy for transferring water from aqueous solution to organic solvent, -0.43 kcal mol(-1) for MeCN and -1.47 kcal mol(-1) for DMF, and the potential of the H(+)/H2 couple, - 0.028 V in MeCN and -0.662 V in DMF. The H(+)/H2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O2/H2O couple has been extended to the CO2/CO and CO2/CH4 couples to give values of -0.12 and +0.15 V in MeCN and -0.73 and -0.48 V in DMF, respectively. Extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol(-1) for acetonitrile and +0.6 kcal mol(-1) for DMF.

Synthesis, structure, and properties of a T-shaped 14-electron stiboranyl-gold complex.

A cyclic stiboranyl-gold complex (1) supported by two 1,8-naphthalenediyl linkers has been synthesized and structurally characterized. The gold atom of this complex adopts a T-shaped geometry and is separated from the antimony center by only 2.76 Å. Surprisingly, the trivalent gold atom of this complex is involved in an aurophilic interaction, a phenomenon typically only observed for monovalent gold complexes. This phenomenon indicates that the stiboranyl ligand possesses strong σ-donating properties making the trivalent gold atom of 1 electron rich. This view is supported by DFT calculations as well as Au L(3)- and Sb K-edge XANES spectra which reveal that 1 may also be described as an aurate-stibonium derivative. In agreement with this view, complex 1 shows no reactivity toward the halides Cl(-), Br(-), and I(-). It does, however, rapidly react with F(-) to form an unprecedented anionic aurate fluorostiborane complex ([2](-)) which has been isolated as the tetra-n-butylammonium salt. The increased coordination number of the antimony center in this anionic complex ([2](-)) does not notably affect the Au-Sb separation (2.77 Å) or the geometry at the gold atom which remains T-shaped.

The importance of precursor and successor complex formation in a bimolecular proton-electron transfer reaction.

The transfer of a proton and an electron from the hydroxylamine 1-hydroxyl-2,2,6,6-tetramethylpiperidine (TEMPOH) to [Co(III)(Hbim)(H(2)bim)(2)](2+) (H(2)bim = 2,2'-biimidazoline) has an overall driving force of DeltaG degrees = -3.0 +/- 0.4 kcal mol(-1) and an activation barrier of DeltaG(degrees) = 21.9 +/- 0.2 kcal mol(-1). Kinetic studies implicate a hydrogen-bonded "precursor complex" at high [TEMPOH], prior to proton-electron (hydrogen-atom) transfer. In the reverse direction, [Co(II)(H(2)bim)(3)](2+) + TEMPO, a similar "successor complex" was not observed, but upper and lower limits on its formation have been estimated. The energetics of formation of these encounter complexes are the dominant contributors to the overall energetics in this system: DeltaG degrees ' for the proton-electron transfer step is only -0.3 +/- 0.9 kcal mol(-1). Thus, formation of the precursor and successor complexes can be a significant component of the thermochemistry for intermolecular proton-electron transfer, particularly in the low-driving-force regime, and should be included in quantitative analyses.

Trends in ground-state entropies for transition metal based hydrogen atom transfer reactions.

Reported herein are thermochemical studies of hydrogen atom transfer (HAT) reactions involving transition metal H-atom donors M(II)LH and oxyl radicals. [Fe(II)(H(2)bip)(3)](2+), [Fe(II)(H(2)bim)(3)](2+), [Co(II)(H(2)bim)(3)](2+), and Ru(II)(acac)(2)(py-imH) [H(2)bip = 2,2'-bi-1,4,5,6-tetrahydropyrimidine, H(2)bim = 2,2'-bi-imidazoline, acac = 2,4-pentandionato, py-imH = 2-(2'-pyridyl)imidazole)] each react with TEMPO (2,2,6,6-tetramethyl-1-piperidinoxyl) or (t)Bu(3)PhO(*) (2,4,6-tri-tert-butylphenoxyl) to give the deprotonated, oxidized metal complex M(III)L and TEMPOH or (t)Bu(3)PhOH. Solution equilibrium measurements for the reaction of [Co(II)(H(2)bim)(3)](2+) with TEMPO show a large, negative ground-state entropy for hydrogen atom transfer, -41 +/- 2 cal mol(-1) K(-1). This is even more negative than the DeltaS(o)(HAT) = -30 +/- 2 cal mol(-1) K(-1) for the two iron complexes and the DeltaS(o)(HAT) for Ru(II)(acac)(2)(py-imH) + TEMPO, 4.9 +/- 1.1 cal mol(-1) K(-1), as reported earlier. Calorimetric measurements quantitatively confirm the enthalpy of reaction for [Fe(II)(H(2)bip)(3)](2+) + TEMPO, thus also confirming DeltaS(o)(HAT). Calorimetry on TEMPOH + (t)Bu(3)PhO(*) gives DeltaH(o)(HAT) = -11.2 +/- 0.5 kcal mol(-1) which matches the enthalpy predicted from the difference in literature solution BDEs. A brief evaluation of the literature thermochemistry of TEMPOH and (t)Bu(3)PhOH supports the common assumption that DeltaS(o)(HAT) approximately 0 for HAT reactions of organic and small gas-phase molecules. However, this assumption does not hold for transition metal based HAT reactions. The trend in magnitude of |DeltaS(o)(HAT)| for reactions with TEMPO, Ru(II)(acac)(2)(py-imH) << [Fe(II)(H(2)bip)(3)](2+) = [Fe(II)(H(2)bim)(3)](2+) < [Co(II)(H(2)bim)(3)](2+), is surprisingly well predicted by the trends for electron transfer half-reaction entropies, DeltaS(o)(ET), in aprotic solvents. This is because both DeltaS(o)(ET) and DeltaS(o)(HAT) have substantial contributions from vibrational entropy, which varies significantly with the metal center involved. The close connection between DeltaS(o)(HAT) and DeltaS(o)(ET) provides an important link between these two fields and provides a starting point from which to predict which HAT systems will have important ground-state entropy effects.

Nitroxyl radical plus hydroxylamine pseudo self-exchange reactions: tunneling in hydrogen atom transfer.

Bimolecular rate constants have been measured for reactions that involve hydrogen atom transfer (HAT) from hydroxylamines to nitroxyl radicals, using the stable radicals TEMPO(*) (2,2,6,6-tetramethylpiperidine-1-oxyl radical), 4-oxo-TEMPO(*) (2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl radical), di-tert-butylnitroxyl ((t)Bu(2)NO(*)), and the hydroxylamines TEMPO-H, 4-oxo-TEMPO-H, 4-MeO-TEMPO-H (2,2,6,6-tetramethyl-N-hydroxy-4-methoxy-piperidine), and (t)Bu(2)NOH. The reactions have been monitored by UV-vis stopped-flow methods, using the different optical spectra of the nitroxyl radicals. The HAT reactions all have |DeltaG (o)| < or = 1.4 kcal mol(-1) and therefore are close to self-exchange reactions. The reaction of 4-oxo-TEMPO(*) + TEMPO-H --> 4-oxo-TEMPO-H + TEMPO(*) occurs with k(2H,MeCN) = 10 +/- 1 M(-1) s(-1) in MeCN at 298 K (K(2H,MeCN) = 4.5 +/- 1.8). Surprisingly, the rate constant for the analogous deuterium atom transfer reaction is much slower: k(2D,MeCN) = 0.44 +/- 0.05 M(-1) s(-1) with k(2H,MeCN)/k(2D,MeCN) = 23 +/- 3 at 298 K. The same large kinetic isotope effect (KIE) is found in CH(2)Cl(2), 23 +/- 4, suggesting that the large KIE is not caused by solvent dynamics or hydrogen bonding to solvent. The related reaction of 4-oxo-TEMPO(*) with 4-MeO-TEMPO-H(D) also has a large KIE, k(3H)/k(3D) = 21 +/- 3 in MeCN. For these three reactions, the E(aD) - E(aH) values, between 0.3 +/- 0.6 and 1.3 +/- 0.6 kcal mol(-1), and the log(A(H)/A(D)) values, between 0.5 +/- 0.7 and 1.1 +/- 0.6, indicate that hydrogen tunneling plays an important role. The related reaction of (t)Bu(2)NO(*) + TEMPO-H(D) in MeCN has a large KIE, 16 +/- 3 in MeCN, and very unusual isotopic activation parameters, E(aD) - E(aH) = -2.6 +/- 0.4 and log(A(H)/A(D)) = 3.1 +/- 0.6. Computational studies, using POLYRATE, also indicate substantial tunneling in the (CH(3))(2)NO(*) + (CH(3))(2)NOH model reaction for the experimental self-exchange processes. Additional calculations on TEMPO((*)/H), (t)Bu(2)NO((*)/H), and Ph(2)NO((*)/H) self-exchange reactions reveal why the phenyl groups make the last of these reactions several orders of magnitude faster than the first two. By inference, the calculations also suggest why tunneling appears to be more important in the self-exchange reactions of dialkylhydroxylamines than of arylhydroxylamines.

Luminescent InP Quantum Dots with Tunable Emission by Post-Synthetic Modification with Lewis Acids.

We demonstrate the ability of M(2+) Lewis acids (M = Cd, Zn) to dramatically enhance the photoluminescence quantum yield (PL QY) of InP quantum dots. The addition of cadmium and zinc is additionally found to red- and blue-shift, respectively, the lowest energy absorption and emission of InP quantum dots while maintaining particle size. This treatment results in a facile strategy to post-synthetically tune the luminescence color in these materials. Optical and structural characterization (XRD, TEM, XAS, ICP) have led us to identify the primary mechanism of PL turn-on as surface passivation of phosphorus dangling bonds, affording PL QYs up to 49% without the growth of a type I shell or the addition of HF. This route to PL enhancement and color tuning may prove useful as a standalone treatment or as a complement to shelling strategies.

Large ground-state entropy changes for hydrogen atom transfer reactions of iron complexes.

Reported herein are the hydrogen atom transfer (HAT) reactions of two closely related dicationic iron tris(alpha-diimine) complexes. FeII(H2bip) (iron(II) tris[2,2'-bi-1,4,5,6-tetrahydropyrimidine]diperchlorate) and FeII(H2bim) (iron(II) tris[2,2'-bi-2-imidazoline]diperchlorate) both transfer H* to TEMPO (2,2,6,6-tetramethyl-1-piperidinoxyl) to yield the hydroxylamine, TEMPO-H, and the respective deprotonated iron(III) species, FeIII(Hbip) or FeIII(Hbim). The ground-state thermodynamic parameters in MeCN were determined for both systems using both static and kinetic measurements. For FeII(H2bip) + TEMPO, DeltaG degrees = -0.3 +/- 0.2 kcal mol-1, DeltaH degrees = -9.4 +/- 0.6 kcal mol-1, and DeltaS degrees = -30 +/- 2 cal mol-1 K-1. For FeII(H2bim) + TEMPO, DeltaG degrees = 5.0 +/- 0.2 kcal mol-1, DeltaH degrees = -4.1 +/- 0.9 kcal mol-1, and DeltaS degrees = -30 +/- 3 cal mol-1 K-1. The large entropy changes for these reactions, |TDeltaS degrees | = 9 kcal mol-1 at 298 K, are exceptions to the traditional assumption that DeltaS degrees approximately 0 for simple HAT reactions. Various studies indicate that hydrogen bonding, solvent effects, ion pairing, and iron spin equilibria do not make major contributions to the observed DeltaS degrees HAT. Instead, this effect arises primarily from changes in vibrational entropy upon oxidation of the iron center. Measurement of the electron-transfer half-reaction entropy, |DeltaS degrees Fe(H2bim)/ET| = 29 +/- 3 cal mol-1 K-1, is consistent with a vibrational origin. This conclusion is supported by UHF/6-31G* calculations on the simplified reaction [FeII(H2N=CHCH=NH2)2(H2bim)]2+...ONH2 left arrow over right arrow [FeII(H2N=CHCH=NH2)2(Hbim)]2+...HONH2. The discovery that DeltaS degrees HAT can deviate significantly from zero has important implications on the study of HAT and proton-coupled electron-transfer (PCET) reactions. For instance, these results indicate that free energies, rather than enthalpies, should be used to estimate the driving force for HAT when transition-metal centers are involved.

Models for proton-coupled electron transfer in photosystem II.

The coupling of proton and electron transfers is a key part of the chemistry of photosynthesis. The oxidative side of photosystem II (PS II) in particular seems to involve a number of proton-coupled electron transfer (PCET) steps in the S-state transitions. This mini-review presents an overview of recent studies of PCET model systems in the authors' laboratory. PCET is defined as a chemical reaction involving concerted transfer of one electron and one proton. These are thus distinguished from stepwise pathways involving initial electron transfer (ET) or initial proton transfer (PT). Hydrogen atom transfer (HAT) reactions are one class of PCET, in which H(+) and e (-) are transferred from one reagent to another: AH + B --> A + BH, roughly along the same path. Rate constants for many HAT reactions are found to be well predicted by the thermochemistry of hydrogen transfer and by Marcus Theory. This includes organic HAT reactions and reactions of iron-tris(alpha-diimine) and manganese-(mu-oxo) complexes. In PS II, HAT has been proposed as the mechanism by which the tyrosine Z radical (Y(Z)*) oxidizes the manganese cluster (the oxygen evolving complex, OEC). Another class of PCET reactions involves transfer of H(+) and e (-) in different directions, for instance when the proton and electron acceptors are different reagents, as in AH-B + C(+) --> A-HB(+) + C. The oxidation of Y(Z) by the chlorophyll P680 + has been suggested to occur by this mechanism. Models for this process - the oxidation of phenols with a pendent base - are described. The oxidation of the OEC by Y(Z)* could also occur by this second class of PCET reactions, involving an Mn-O-H fragment of the OEC. Initial attempts to model such a process using ruthenium-aquo complexes are described.

Hydrogen atom transfer from iron(II)-tris[2,2'-bi(tetrahydropyrimidine)] to TEMPO: a negative enthalpy of activation predicted by the Marcus equation.

The transfer of a hydrogen atom from iron(II)-tris[2,2'-bi(tetrahydropyrimidine)], [FeII(H2bip)3]2+, to the stable nitroxide, TEMPO, was studied by stopped-flow UV-vis spectrophotometry. The products are the deprotonated iron(III) complex [FeIII(H2bip)2(Hbip)]2+ and the hydroxylamine, TEMPO-H. This reaction can also be referred to as proton-coupled electron transfer (PCET). The equilibrium constant for the reaction is close to 1; thus, the reaction can be driven in either direction. The rate constants for the forward and reverse reactions at 298 K are k1 = 260 +/- 30 M-1 s-1 and k-1 = 150 +/- 20 M-1 s-1. Interestingly, the rate constant for the forward reaction decreases as reaction temperature is increased, implying a negative activation enthalpy: DeltaH1 = -2.7 +/- 0.4 kcal mol-1, DeltaS1 = -57 +/- 8 cal mol-1 K-1. Marcus theory predicts this unusual temperature dependence on the basis of independently measured self-exchange rate constants and equilibrium constants: DeltaHcalcd = -3.5 +/- 0.5 kcal mol-1, DeltaScalcd = -42 +/- 10 cal mol-1 K-1. This result illustrates the value of the Marcus approach for these types of reactions. The dominant contributor to the negative activation enthalpy is the favorable enthalpy of reaction, DeltaH1 degrees = -9.4 +/- 0.6 kcal mol-1, rather than the small negative activation enthalpy for the H-atom self-exchange between the iron complexes.